CN103159869B - Modified conjugated diene rubber, and method and composition thereof - Google Patents
Modified conjugated diene rubber, and method and composition thereof Download PDFInfo
- Publication number
- CN103159869B CN103159869B CN201210368072.2A CN201210368072A CN103159869B CN 103159869 B CN103159869 B CN 103159869B CN 201210368072 A CN201210368072 A CN 201210368072A CN 103159869 B CN103159869 B CN 103159869B
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- CN
- China
- Prior art keywords
- conjugated diene
- diene rubber
- modified conjugated
- properties
- correcting agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920003244 diene elastomer Polymers 0.000 title claims abstract description 117
- 238000000034 method Methods 0.000 title claims description 40
- 239000000203 mixture Substances 0.000 title claims description 27
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 16
- 125000004450 alkenylene group Chemical group 0.000 claims abstract description 13
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 80
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 64
- 239000000377 silicon dioxide Substances 0.000 claims description 32
- 239000002585 base Substances 0.000 claims description 31
- 229920001971 elastomer Polymers 0.000 claims description 24
- 239000005060 rubber Substances 0.000 claims description 24
- 235000012239 silicon dioxide Nutrition 0.000 claims description 24
- 229960001866 silicon dioxide Drugs 0.000 claims description 24
- 229910052783 alkali metal Inorganic materials 0.000 claims description 20
- 150000001340 alkali metals Chemical class 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 150000001993 dienes Chemical group 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 14
- 230000008878 coupling Effects 0.000 claims description 12
- 238000010168 coupling process Methods 0.000 claims description 12
- 238000005859 coupling reaction Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 239000000470 constituent Substances 0.000 claims description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 claims description 6
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 5
- 229960002887 deanol Drugs 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 abstract description 2
- 239000003607 modifier Substances 0.000 abstract 4
- 125000003342 alkenyl group Chemical group 0.000 abstract 2
- 239000001301 oxygen Substances 0.000 abstract 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract 1
- 125000002723 alicyclic group Chemical group 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- -1 silica compound Chemical class 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 25
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 150000002500 ions Chemical class 0.000 description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000004073 vulcanization Methods 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- 238000005728 strengthening Methods 0.000 description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 description 6
- 238000005987 sulfurization reaction Methods 0.000 description 6
- FWBQUXLXFQMKME-UHFFFAOYSA-N trimethoxy(methyl)silane Chemical compound CO[Si](C)(OC)OC.CO[Si](C)(OC)OC FWBQUXLXFQMKME-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- ASHGTJPOSUFTGB-UHFFFAOYSA-N 3-methoxyphenol Chemical compound COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000004807 desolvation Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 101150065749 Churc1 gene Proteins 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 102100038239 Protein Churchill Human genes 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000000413 hydrolysate Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical group CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- MENUHMSZHZBYMK-UHFFFAOYSA-N 2-cyclohexylethenylbenzene Chemical class C1CCCCC1C=CC1=CC=CC=C1 MENUHMSZHZBYMK-UHFFFAOYSA-N 0.000 description 2
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- SHGUVJPXKKRMRP-UHFFFAOYSA-N [O].CCCC Chemical compound [O].CCCC SHGUVJPXKKRMRP-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 229960002380 dibutyl phthalate Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- ZHIDJOQMCAERGH-UHFFFAOYSA-N prop-1-enylbenzene prop-2-enylbenzene Chemical compound CC=CC1=CC=CC=C1.C(=C)CC1=CC=CC=C1 ZHIDJOQMCAERGH-UHFFFAOYSA-N 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical group [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- WIHIUTUAHOZVLE-UHFFFAOYSA-N 1,3-diethoxypropan-2-ol Chemical compound CCOCC(O)COCC WIHIUTUAHOZVLE-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- BCJXJKODKVRTEW-UHFFFAOYSA-N 1-ethenylanthracene Chemical compound C(=C)C1=CC=CC2=CC3=CC=CC=C3C=C12.C(=C)C1=CC=CC2=CC3=CC=CC=C3C=C12 BCJXJKODKVRTEW-UHFFFAOYSA-N 0.000 description 1
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 description 1
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- DMCINEDFOKMBFI-UHFFFAOYSA-N 3,4-dimethylidenehexa-1,5-diene Chemical compound C=CC(=C)C(=C)C=C DMCINEDFOKMBFI-UHFFFAOYSA-N 0.000 description 1
- WMLZREYCISVLDD-UHFFFAOYSA-N 5-methylidenehepta-1,3,6-triene Chemical compound C=CC=CC(=C)C=C WMLZREYCISVLDD-UHFFFAOYSA-N 0.000 description 1
- AMOCQVGMBLFIRA-UHFFFAOYSA-N C(=C)C1=C(C=CC=C1)C1=CC=CC=C1.C(=C)C1=C(C=CC=C1)C1=CC=CC=C1 Chemical group C(=C)C1=C(C=CC=C1)C1=CC=CC=C1.C(=C)C1=C(C=CC=C1)C1=CC=CC=C1 AMOCQVGMBLFIRA-UHFFFAOYSA-N 0.000 description 1
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- 244000043261 Hevea brasiliensis Species 0.000 description 1
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- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
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- HIJMOEODDGNLNS-UHFFFAOYSA-N [Li]CCCC.[Li]CCCC Chemical compound [Li]CCCC.[Li]CCCC HIJMOEODDGNLNS-UHFFFAOYSA-N 0.000 description 1
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- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- KHPJWAWPONWPCY-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1.CCC=CC1=CC=CC=C1 KHPJWAWPONWPCY-UHFFFAOYSA-N 0.000 description 1
- KSGVXQNNSWGIIB-UHFFFAOYSA-N buta-1,3-dien-2-ylbenzene Chemical compound C1(=CC=CC=C1)C(=C)C=C.C1(=CC=CC=C1)C(=C)C=C KSGVXQNNSWGIIB-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZPFKRQXYKULZKP-UHFFFAOYSA-N butylidene Chemical group [CH2+]CC[CH-] ZPFKRQXYKULZKP-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229940105289 carbon black Drugs 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000012936 vulcanization activator Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
- C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/22—Incorporating nitrogen atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/25—Incorporating silicon atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/06—Butadiene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/08—Isoprene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/54—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof
- C08F4/56—Alkali metals being the only metals present, e.g. Alfin catalysts
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a modified conjugated diene rubber, which is prepared by the following steps: reacting the conjugated diene rubber containing alkali metal ions with a first modifier, wherein the first modifier has the following structural formula , wherein R1、R2、R3Each independently selected from C1~C12Alkyl and alkenyl of, and C6~C12Aryl radical, and R4Is selected from C1~C12Alkyl, alkenyl, alkoxy, and C6~C12An aromatic group; and a step (b): adding a second modifier after step (a), the second modifier having formula (II) wherein R5Is selected from C1~C12Alkylene, alkenylene, alicyclic group and C6~C12Aryl radical, Y is selected from C1~C12Oxygen-containing group of and (C)1~C12With Y being directly linked to R by its oxygen or nitrogen atom5Is bonded to the carbon atom.
Description
Technical field
The present invention relates to a kind of conjugated diene rubber, particularly carry out the conjugated diene rubber of modification with two kinds of properties-correcting agent.
Background technology
Solution polymerized butadiene styrene rubber (solution styrene butadiene rubber, SSBR) is formed by divinyl and styrene units.First propose batch processing procedure and Firestone company proposition continous way processing procedure by Phillips company of the U.S., and take the lead in realizing suitability for industrialized production.Have more excellent mechanical property and rolling resistance because solution polymerized butadiene styrene rubber has than emulsion polymerized styrene butadiene rubber (emulsion styrene butadiene rubber, ESBR), thus more can be widely used in automotive industry and other rubber items.
Along with recent automobile reduces the requirement of oil consumption, the property requirements of the elastomeric material for tire is also increased thereupon.Conjugated diene rubber has low rolling impedance, excellent abrasion impedance, and produces more excellent control stability because of anti-slippery, and its demand property is increased.On the other hand, industry is more set forth in the rubber combination of tire and adds silicon-dioxide mixing material (silica compound) or silicon-dioxide and carbon black (carbon black) using as strengthening agent.Tire tread containing silicon-dioxide or silicon-dioxide and carbon black stock has low rolling impedance and anti-slippery and produce more excellent control stability.
For making conjugated diene rubber can do better to combine with strengthening agent, industry has produced the technology of much modified conjugated diene rubber.US Patent No. 4,185,042 discloses a kind of coupler for SBS block copolymer, will containing the polymkeric substance of lithium with react containing silicon coupling agent, the coupling rate >90% of the polymkeric substance obtained and being present in polymkeric substance without Si-OR base.US Patent No. 5,219,938 steps disclosing a kind of two benches modification, by use two kinds of properties-correcting agent, first will containing the diene polymer chain end of lighium polymer and coupler R
nsiCl
4-nor R
nsnCl
4-nreaction, then again with coupler (R
5r
6r
7-Si-(CH
2)
n-N-R
8r
9) reaction modifying.US Patent No. 7,288,594 disclose with the styrene-butadiene rubber(SBR) of two kinds of different silane compound two benches modifications containing lithium.In addition, US Patent No. 7,807,747 disclose with the styrene-butadiene rubber(SBR) of identical silane compound two benches modification containing lithium.
But the most difficulty of its processing procedure of modified conjugated diene rubber synthesized by above-mentioned prior art is complicated and not easily implement, so the problem that industry still needs novel conjugated diene rubber modification technology to produce to solve prior art.
Summary of the invention
An aspect of of the present present invention is the manufacture method providing a kind of modified conjugated diene rubber, comprises: step (a): the conjugated diene rubber of alkali metal containing ion and the first properties-correcting agent are reacted, and this first properties-correcting agent has following structural formula (I)
Wherein R
1, R
2, R
3be selected from independently of one another containing C
1~ C
12alkyl and thiazolinyl and C
6~ C
12aromatic base, and R
4be selected from C
1~ C
12alkyl, thiazolinyl and alkoxyl group and C
6~ C
12aromatic base; And
Step (b): add the second properties-correcting agent after this step (a), this second properties-correcting agent has following structural formula (II)
HO-R
5-Y (II)
Wherein R
5be selected from C
1~ C
12alkylidene group (alkylene), alkenylene (alkenylene), alicyclic radical and C
6~ C
12aromatic base, Y is selected from C
1~ C
12oxy radical and C
1~ C
12nitrogen-containing group, Y is with its Sauerstoffatom or its nitrogen-atoms directly and R
5carbon atom combine.
Another aspect of the present invention is to provide a kind of modified conjugated diene rubber, and it is made with aforesaid manufacture method; And a kind of conjugated diene rubber composition, comprise this modified conjugated diene rubber and silicon-dioxide (silica).
The present invention is to provide a kind of modified conjugated diene rubber again on the other hand, and this modified conjugated diene rubber is following structural formula (III) or structural formula (IV):
The polymeric chain that D is formed for conjugated diene unit or conjugated diene unit and vinyl aromatic unit,
Wherein R
4be selected from C
1~ C
12alkyl, thiazolinyl, alkoxyl group and C
6~ C
12aromatic base, R
5be selected from C
1~ C
12alkylidene group (alkylene), alkenylene (alkenylene), alicyclic radical and C
6~ C
12aromatic base, Y is selected from C
1~ C
12oxy radical and C
1~ C
12nitrogen-containing group, Y is with its Sauerstoffatom or its nitrogen-atoms directly and R
5carbon atom combine; And a kind of conjugated diene rubber composition, comprise this modified conjugated diene rubber and silicon-dioxide (silica).
Embodiment
For making the present invention and the claim that will advocate thereof be more fully understood, the preferred embodiments of the invention of below demonstrating.For avoiding fuzzy content of the present invention, below illustrating and may omit known element, associated materials and correlation processing technique thereof.The following stated is only the preferred embodiments of the invention, and is not used to limit claim of the present invention; Under all other does not depart from disclosed spirit, the equivalence that completes changes or modifies, and all should be included in described claim.
Polyreaction: the conjugated diene rubber forming alkali metal containing ion
The manufacture method of the conjugated diene rubber of formation alkali metal containing ion of the present invention comprises in a suitable solvent, utilize anionic polymerization, using organic alkali metal compound as initiator polymerized conjugated diene monomer or conjugate diene monomer and vinyl aromatic monomers to form the conjugated diene rubber of alkali metal containing ion.
Polymkeric substance of the present invention can be conjugate diene monomer polymkeric substance, or is the multipolymer of conjugate diene monomer (such as divinyl (butadiene) or isoprene (isoprene)) and vinyl aromatic monomers (such as vinylbenzene (styrene) or vinyl toluene (methyl styrene)).The polymerization single polymerization monomer of conjugated diene rubber of the present invention is not limited in divinyl, isoprene and vinylbenzene, and above-mentioned any suitable derivative all can be used for the present invention.For example, conjugate diene monomer is independently selected from following items: 1,3-divinyl (1,3-butadiene), 2,3-dimethyl-1,3-divinyl (2,3-dimethyl-1,3-butadiene), 3-butyl-1,3-octadiene (3-butyl-1,3-octadiene), isoprene (isoprene), 1-dimethyl butadiene (1-methylbutadiene), 2-phenyl-1,3-butadiene (2-phenyl-1,3-butadiene) and above-mentioned every any combination thereof.Vinyl aromatic monomers can independently selected from following items: vinylbenzene (styrene), vinyl toluene (methylstyrene) and all isomers thereof, ethyl styrene (ethylstyrene) and all isomers thereof, cyclohexylstyrenes (cyclohexylstyrene), vinyl biphenyl (vinyl biphenyl), 1-vinyl-5-hexyl naphthalene (1-vinyl-5-hexyl naphthalene), vinyl naphthalene (vinyl naphthalene), vinyl anthracene (vinyl anthracene) and above-mentioned every any combination thereof.
When being polymerized, using organolithium compound to be preferably select as initiator, therefore can obtain it has carbon lithium ion alkalimetal ion conjugated diene rubber at molecule chain end.The object lesson of organolithium initiator comprises n-propyl lithium, isopropyl lithium, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, n-pentyl lithium, phenyl lithium, tolyl lithium etc., is preferably n-Butyl Lithium.
The suitable solvent of polyreaction is as inert organic solvents, it means the solvent that can not participate in the polymerization reacting, this kind solvent comprises butane, Trimethylmethane, Skellysolve A, iso-pentane, 2, the aliphatic hydrocarbon of 2,4-trimethylpentane, isohexane, normal hexane, isoheptane, normal heptane, octane-iso, octane; Or the cycloparaffin series of picture hexanaphthene, methylcyclohexane, ethylcyclohexane, pentamethylene, suberane, methylcyclopentane; Or the arene compounds such as benzene,toluene,xylene, ethylbenzene, diethylbenzene and propyl benzene, are applicable to preferably of the present invention for hexanaphthene.The polymeric solution concentration of conjugated diene rubber is generally 5% to 35%, is preferably 10% to 30%.In the ordinary course of things, use inert organic solvents as solvent if simple, the rate of polymerization of vinyl aromatic or conjugated diolefine is comparatively slow and both polyreaction sex differernce is quite large, now can overcome by the mode adding polar solvent.The object lesson being applicable to polar solvent of the present invention comprises ether compound and the Tetramethyl Ethylene Diamines such as tetrahydrofuran (THF), diethyl ether, ring amyl ether, dipropyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, glycol ether, dme, methyl ethyl ether, is preferably tetrahydrofuran (THF) and diethyl ether.
The starting temperature of polymerization can in 10 DEG C to 80 DEG C, and outlet temperature can in 30 DEG C to 150 DEG C, and method for temperature manipulation can use adiabatic reaction mode, also can adopt thermostatic control, or adopt the part type of cooling.
According to each embodiment of the present invention, after being polymerized but the polymkeric substance initial number average molecular weight (Mi) not yet reacted with properties-correcting agent is 80kg/mole to 2000kg/mole, be preferable between 100kg/mole to 1500kg/mole, more preferably between 150kg/mole to 1000kg/mole.The mensuration of number-average molecular weight uses hydrogel permeation layer analyzer (gel permeation chromatography; GPC), this is the conventional practice of those skilled in the art.
Add properties-correcting agent
Modified-reaction of the present invention uses two kinds of properties-correcting agent to form modified conjugated diene rubber, its method for making comprises step (a): the conjugated diene rubber of alkali metal containing ion and the first properties-correcting agent are reacted, and this first properties-correcting agent has following structural formula (I):
From structural formula (I), the first properties-correcting agent is siloxanes, wherein R
1, R
2, R
3be selected from independently of one another containing C
1~ C
12alkyl and thiazolinyl and C
6~ C
12aromatic base, and R
4be selected from C
1~ C
12alkyl, thiazolinyl and alkoxyl group and C
6~ C
12aromatic base.In each example of the first properties-correcting agent of the present invention, R
1, R
2, R
3, R
4be respectively alkyl separately, example has methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, hexyl, 2-ethylhexyl; R
1, R
2, R
3, R
4be respectively thiazolinyl separately, example has vinyl, propenyl, n-butene base, isobutenyl, pentenyl, hexenyl; R
1, R
2, R
3, R
4the example being respectively aromatic base separately has phenyl, tolyl, ethylbenzene, xylyl, propyl phenyl.R
4example for alkoxyl group has first alkoxyl group, second alkoxyl group, the third alkoxyl group, normal butane oxygen base, isobutyl alkoxyl group.The example that the spy of the first properties-correcting agent is good is R
1, R
2, R
3, R
4be all trimethoxy (methyl) silane (Trimethoxy (methyl) silane) of methyl.
The conjugated diene rubber of the alkali metal containing ion of step (a) can be the polymkeric substance that polymerization procedure described above is formed, or otherwise formed suitable polymkeric substance.When the modified-reaction of step (a) carries out, the first properties-correcting agent is combined with the diene chain end of the conjugated diene rubber of alkali metal containing ion.The molar ratio of the conjugated diene rubber of the first properties-correcting agent and alkali metal containing ion is >=0.5, is preferably >=0.6, be more preferably >=0.7, but must lower than 10.
Modified-reaction method of the present invention more comprises step (b): after this step (a), add the second properties-correcting agent, and the second properties-correcting agent has following structural formula (II)
HO-R
5-Y (II)
Wherein R
5be selected from C
1~ C
12alkylidene group (alkylene), alkenylene (alkenylene), alicyclic radical and C
6~ C
12aromatic base, Y is selected from C
1~ C
12oxy radical and C
1~ C
12nitrogen-containing group, Y is with its Sauerstoffatom or its nitrogen-atoms directly and R
5carbon atom combine.Be the heteroatomic alcohols with O or N by known second properties-correcting agent of structural formula (II).R
5example for alkylidene group (alkylene) has ethylidene (ethylene ， – CH
2cH
2-), propylidene (-CH
2cH
2cH
2-), butylidene (-CH
2cH
2cH
2cH
2-); R
5for alkenylene (alkenylene) example has vinylidene (vinylene ,-CHCH-), propenylidene (-CH=CHCH
2-), crotonylidene (-CH=CHCH
2cH
2-), sub-hexenyl (-CH
2cH=CHCH
2cH
2cH
2-); R
5example for aromatic base has phenyl, tolyl, ethylbenzene, xylyl, propyl phenyl; R
5example for alicyclic radical has cyclopropane base, tetramethylene base, pentamethylene base, cyclohexyl, suberane base.Y is C
1~ C
12the example of oxy radical have first alkoxyl group, second alkoxyl group, the third alkoxyl group, normal butane oxygen base, isobutyl alkoxyl group.Y is C
1~ C
12the example of nitrogen-containing group have diethylin, dimethylin, the first and second amidos.The example that the spy of the second properties-correcting agent is good is 3-methoxyl group phenol (3-methoxyphenol) or dimethylaminoethanol (dimethylaminoethanol).The molar ratio of the conjugated diene rubber of the second properties-correcting agent and alkali metal containing ion is >=0.5, is preferably >=0.6, be more preferably >=0.7, but must lower than 10.
Water contact reacts
Conjugated diene rubber of the present invention as above-mentioned add the first properties-correcting agent and the second properties-correcting agent after, it can be made to contact with water, and wherein the ratio of conjugated diene rubber and the water yield is determined by required situation.If more improve the stability of its mooney viscosity, it can be made to contact with a large amount of water, its method comprises steam stripped (steamstripping) method or other suitable methods.For steam stripped, the conjugated diene rubber solution containing solvent can be made to contact with water, and temperature controls under 90 ° of C, wherein in the water yield and conjugated diene rubber solution, solvent-laden part by weight is more than 0.1, more preferably more than 0.5, be preferably more than 1, and can make pH between 6 ~ 10.Temperature during both contacts can be 20 to 150 DEG C, more preferably 30 to 140 DEG C, is preferably 40 to 130 DEG C, and both times of contact are 5 minutes to 10 hours, are more preferably 10 minutes to 8 hours, it is preferred that 30 minutes to 6 hours.While conjugated diene rubber solution contacts with water or steam, electric heating, warm air or other thermal source desolvations can be utilized afterwards, again through known drying mode, such as: mechanical dehydration, oven drying or tunnel drying (apron dryer) mode process, or such as rubber to be carried out under 110 ° of C hot roller (hot roll) dry.The coupling rate that conjugated diene rubber of the present invention is recording after above-mentioned water contact pairs is 10% ~ 95%, is preferably 20 ~ 80%, is more preferably 25 ~ 75%, most preferably is 30 ~ 70%.
Above-mentioned embodiment illustrates and after the reacted conjugated diene rubber of the first properties-correcting agent is first mixed into the second properties-correcting agent, then will contact preferably with water.But the present invention also comprises utilization proper method makes the second properties-correcting agent and water add simultaneously, or make the embodiment adding the second properties-correcting agent after the reacted conjugated diene rubber of the first properties-correcting agent first contacts with water again.For example, steam stripped can be carried out by through the reacted conjugated diene rubber of the first properties-correcting agent, in steam stripped process, add the second properties-correcting agent; Or first will carry out steam stripped through the reacted conjugated diene rubber of the first properties-correcting agent, after steam stripped, add the second properties-correcting agent again.
Modified-reaction mechanism
About the reaction mechanism of above-mentioned modification rationally estimates as follows:
Step (a): the conjugated diene rubber of alkali metal containing ion and the first properties-correcting agent are reacted
Wherein (A) represents the conjugated diene rubber of alkali metal containing ion lithium (Li), (A) polymeric chain that the D representative in is formed with conjugated diene unit or conjugated diene unit and vinyl aromatic unit, after reacting with the first properties-correcting agent siloxanes (I), the metal ion lithium in conjugated diene rubber (A) replace by the first properties-correcting agent siloxanes (I) and form the conjugated diene rubber (B) with siloxanes.
Step (b): add the second properties-correcting agent (II) after this step (a), just the second properties-correcting agent is only mixed in polymers soln and not yet produces modified-reaction.
Step (c): add water and produce hydrolysis reaction
The process (such as steam stripped) contacted with water with the conjugated diene rubber (B) of siloxanes can be hydrolyzed and react to generate hydrolysate (D).
Step (d): hydrolysate (D) and the second properties-correcting agent (II) react
Hydrolysate (D) will react with the second properties-correcting agent (II), to generate the siloxanes conjugated diene rubber with N or O atom (representing with Y), the polymkeric substance as shown in structural formula (III) or structural formula (IV).From above-mentioned inference, by the first properties-correcting agent, silicone functionalities is introduced conjugated diene rubber, and then the functional group containing N or O atom is introduced the conjugated diene rubber of tool siloxanes by the second properties-correcting agent.
Modified conjugated diene rubber
The modified conjugated diene rubber with following structural formula (III) or structural formula (IV) can be formed after above-mentioned modified-reaction:
Wherein R
4be selected from C
1~ C
12alkyl, thiazolinyl, alkoxyl group and C
6~ C
12aromatic base, R
5be selected from C
1~ C
12alkylidene group (alkylene), alkenylene (alkenylene), alicyclic radical and C
6~ C
12aromatic base, Y is selected from C
1~ C
12oxy radical and C
1~ C
12nitrogen-containing group, Y is with its Sauerstoffatom or its nitrogen-atoms directly and R
5carbon atom combine.In the preferred embodiment, R
4for methyl.Be C at Y
1~ C
12oxy radical preferred embodiment in, Y can be alkyl, aromatic base or thiazolinyl and connects this Sauerstoffatom; Be C at Y
1~ C
12nitrogen-containing group preferred embodiment in, Y can be alkyl, aromatic base or thiazolinyl and connects this nitrogen-atoms.About the example of alkyl, aromatic base, thiazolinyl or alicyclic radical can with reference to the explanation in above-described modified-reaction.In the example of Te Jia ,-the O-R in structural formula (III) and structural formula (IV)
5-Y is-O-(C
6h
4)-OCH
3or-O-CH
2cH
2n (CH
3)
2.
Conjugated diene rubber composition
Modified conjugated diene rubber of the present invention can form a kind of conjugated diene rubber composition by mixing with other rubber constituents.The object lesson of other rubber constituents comprises conventional styrene-butadiene copolymer rubber, polybutadiene rubber, butadiene isoprene copolymer rubber and isoprene-isobutylene rubber.Object lesson more comprises natural rubber, ethylene-propylene copolymer rubber and ethylene-octene copolymer rubber.Above-mentioned composition can two or more patterns mixing application.Composition containing the conjugated diene rubber composition of modified conjugated diene rubber can be, and when the total amount of whole rubber constituent is 100 weight part, the content of modified conjugated diene rubber is preferably at least 10 weight parts, and is more preferably at least 20 weight parts.
Moreover conjugated diene rubber composition of the present invention also can contain additive.The object lesson of additive comprises vulcanizing agent such as sulphur; Vulcanization accelerator such as based on the vulcanization accelerator of thiazolyl (thiazole-based), based on the vulcanization accelerator of thiuram base (thiuram-based) or the vulcanization accelerator based on sulfenamide groups (sulfenamide-based); Vulcanization activator, such as stearic acid or zinc oxide; Organo-peroxide; Strengthening agent such as silicon-dioxide or carbon black; Weighting agent such as calcium carbonate or talcum; Silane coupling agent; Extending oil; Processing aid; Antioxidant; And lubricant etc.
In the example being mixed into conjugated diene rubber composition of the present invention mixing using silicon-dioxide as strengthening agent, when the total amount of whole rubber constituent is 100 weight part, the content of silicon-dioxide is generally 10 weight part to 200 weight parts.Look it from fuel-efficient viewpoint, mixed amount is preferably at least 20 weight parts, and is more preferably at least 30 weight parts.It is looked, preferably no more than 180 weight parts, and more preferably less than 150 weight parts from the viewpoint of reinforcing effect.Silicon-dioxide can be amorphousness synthetic silica, such as, obtain by acidifying (acidification) soluble silicate (such as water glass or silicate and the coprecipitated of aluminate are analysed).Generally speaking, this type of precipitating silicon-dioxide is known to ordinary skill in the art.The BET specific surface area of synthetic silica (precipitating silicon-dioxide), measures with nitrogen, can be such as between scope about 50 to about 300 meters squared per gram, or selectively between scope about 100 to about 250 meters squared per gram.Silicon-dioxide also can have dibutyl phthalate (dibutylphthalate, DBP) absorption value, such as scope between about 100cc/g to about between 500cc/g, preferable range between about 120cc/g to about between 350cc/g.The commercially available synthetic silica of other various business can be considered to be used in the present invention, comprises but is not limited to the commercially available silicon-dioxide of the business such as provided by PPG Industries, such as trade mark Hi-Sil trademark model 210,243 etc.; The commercially available silicon-dioxide of the business provided by Rhodia company, such as marque Zeosil 1165MP and Zeosil165GR; The commercially available silicon-dioxide of the business provided by EVONIK company, such as marque VN2, VN3,7000GR, 9000GR; And the commercially available silicon-dioxide of business to be provided by Huber, such as marque Zeopol 8745.
Be mixed in the example of conjugated diene rubber composition of the present invention using non-silicon-dioxide as strengthening agent, it is looked from the viewpoint of reinforcing effect, when the total amount of whole rubber constituent is 100 weight part, the content of described non-silica reinforcing agent preferably no more than 120 weight parts, and more preferably less than 100 weight parts.Look it from fuel-efficient viewpoint, be preferably at least 1 weight part, and be more preferably at least 3 weight parts.But not the preferred object lesson of silica reinforcing agent is carbon black.
Modified conjugated diene rubber of the present invention mixes with another rubber constituent, additive etc. the method manufacturing conjugated diene rubber composition, can example mixing tank as is known, it similarly is roller, or banbury mixers (Banbury mixer), or Banbury mixer (internal mixer) is in order to mediate the method for (knead) each component.About the condition of mediating, except vulcanizing agent or vulcanization accelerator, when mixed additive, weighting agent, silicon-dioxide and/or other strengthening agents, the temperature of mediating is generally 50 DEG C to 200 DEG C, be preferably 80 DEG C to 150 DEG C, and the time of mediating is generally 30 seconds to 30 minutes, be preferably 1 minute to 30 minutes.When vulcanizing agent or vulcanization accelerator mixing, the temperature of described kneading is no more than 100 DEG C usually, is preferably room temperature to 90 DEG C.The combination mixed by vulcanizing agent or vulcanization accelerator can use the sulfidizing mode of such as press cure (pressvulcanization) to be implemented.The temperature of described sulfidizing is generally 120 DEG C to 200 DEG C, is preferably 140 DEG C to 180 DEG C.
Modified conjugated diene rubber of the present invention and conjugated diene rubber composition thereof can be used in tire, sole, flooring material and vibrations and block material etc., and be particularly suitable for tire, with promote tire tread low rolling impedance and promote anti-slippery and produce control stability and reliability.
By the following processing procedure describing polyreaction of the present invention and modified-reaction with embodiment in detail.
Embodiment 1 (Y is nitrogen-containing group)
There is provided autoclave reactor, initial capacity about 5 liters is with nitrogen filling.Insert the hexanaphthene of 2750 grams, the tetrahydrofuran (THF) of 82.5 grams, the 1,3-butadiene of the vinylbenzene of 100 grams and 390 grams is in autoclave reactor.When the temperature of reactor content reaches 30 ° of C, the n-Butyl Lithium (n-butyl lithium) adding 310 milligrams (4.80mmole) reacts with starting polymerization.Polyreaction is carried out under adiabatic condition, and top temperature is 83 DEG C.When polyreaction almost completes, the 1,3-butadiene adding 10g carries out polyreaction about 5 minutes again.Then trimethoxy (methyl) silane (Trimethoxy (methyl) silane, hereinafter referred to as M1) adding 1.308mg (9.60mmole) carries out the first paragraph modified-reaction of about 10 minutes.And then the dimethylaminoethanol (dimethylaminoethanol, hereinafter referred to as M2) adding 1.28g (14.4mmole) carries out mixing in about 10 minutes.Then, add 2,6 ditertiary butyl p cresol (2,6-di-tert-butyl-p-cresol) and make reaction terminating in polymers soln.Then, by polymers soln desolvation, modified conjugated diene rubber is contacted with large water gaging, then utilize feasible thermal source desolvation and moisture.Under 90 ° of C, implement steam stripping (steam stripping) step, the part by weight of the water yield and solvent be more than 1, pH between 6 ~ 10, continue 3 hours.Then obtained rubber is carried out under 110 ° of C hot rolling (hot roll) dry.The rubber of embodiment 1 is defined as through the modified conjugated diene rubber of above-mentioned each step.First properties-correcting agent of embodiment 1 and the second properties-correcting agent respectively with the molar ratio of the conjugated diene rubber of alkali metal containing ion, initial molecular weight (Mi), and obtain product various character list in detail in accompanying table one.
Embodiment 2 (Y is nitrogen-containing group)
The step of embodiment 2 can the step of reference example 1, and it all uses same solvent and reactant, and the difference of reaction conditions is only the content of each reactant.The reaction conditions of each embodiment, as the molar ratio of the conjugated diene rubber of properties-correcting agent and alkali metal containing ion, initial molecular weight (Mi), and obtain product various character list in detail in accompanying table two.
Embodiment 3-4 (Y is oxy radical)
The step of embodiment 3-4 can the step of reference example 1, and the difference of reaction conditions is only that second properties-correcting agent of embodiment 3-4 uses 3-methoxyl group phenol (3-methoxyphenol, hereinafter referred to as M3).The reaction conditions of each embodiment, as the first properties-correcting agent and the second properties-correcting agent respectively with the molar ratio of the conjugated diene rubber of alkali metal containing ion, initial molecular weight (Mi), and obtain product various character list in detail in accompanying table two.Embodiment 3-4 its all use same solvent and reactant, the difference of reaction conditions is only the content of each reactant.
Comparative example 1
Polymerization procedure is with embodiment 1.During modified-reaction, carry out about 10 minutes with the trimethoxy of 0.327mg (2.40mmole) (methyl) silane (Trimethoxy (methyl) silane, hereinafter referred to as M1).Then, do not add the second properties-correcting agent, directly add 2,6 ditertiary butyl p cresol (2,6-di-tert-butyl-p-cresol) and make reaction terminating in polymers soln.After this polymers soln rubber desolvation, under 110 ° of C, carry out the conjugated diene rubber that hot roller (hot roll) drying can obtain modification, be defined as the rubber of comparative example 1.The molar ratio of the properties-correcting agent of comparative example 1 and the conjugated diene rubber of alkali metal containing ion, initial molecular weight (Mi), and obtain product various character list in detail in accompanying table one.
Comparative example 2 and 3
The step of comparative example 2 to 3 can with reference to the step of comparative example 1, and essential difference is that reactant species is different.The properties-correcting agent that comparative example 1 uses is trimethoxy (methyl) silane (Trimethoxy (methyl) silane, M1); The properties-correcting agent that comparative example 2 uses is tetraethoxysilane (tetraethoxysilane, TEOS); The properties-correcting agent that comparative example 3 uses is tetramethoxy-silicane (tetramethoxysilane, TMOS).The molar ratio of the properties-correcting agent of each comparative example and the conjugated diene rubber of alkali metal containing ion, the reaction conditionss such as initial molecular weight (Mi) and the rear products therefrom characteristic of reaction are listed in accompanying table one in detail.
Below illustrate that the rubber that each embodiment above-mentioned for the present invention obtains is made into conjugated diene rubber composition also forms sulfuration sheet plate film further to test the method for loss tangent.
Get each embodiment rubber of 100 weight parts, silicon-dioxide (the trade name Ultrasil7000GR of 78.4 weight parts, manufactured by EVONIK company), silane coupling agent (the trade name Si69 of 6.9 weight parts, manufactured by EVONIK company), extending oil (the TDAE of 50.0 weight parts, manufactured by IRPC company), the antioxidant (trade name Antigene 3C) of 1.5 weight parts, the stearic acid of 2 weight parts, the zinc oxide of 2 weight parts, the wax of 1.5 weight parts, the sulphur of 1.4 weight parts, and 2 weight part vulcanization accelerator (each 1 weight part of trade name CZ and D) mediate to form composition.Described plate film by two roller machine die castings plate film in blocks, can be heated to 160 DEG C, maintain 45 minutes, carry out sulfuration by described composition, obtains sulfuration sheet plate film thus.
The loss tangent of described sulfuration sheet plate film at 60 DEG C (loss tangent, tan δ (60 DEG C)) can measure by use viscoelastic instrument (viscoelastometer), and measurement condition is the strain of 1% and the frequency of 10Hz.Such as, using comparative example 2 as standard, make comparative example 2 be 100%, then higher person of embodiment value, energy-saving effect is better.The loss tangent of described sulfuration sheet plate at 0 DEG C (tan δ (0 DEG C)) can measure by use viscoelastic instrument, and measurement condition is the strain of 0.5% and the frequency of 10Hz.Such as, using comparative example as standard, make comparative example 2 be 100%, then higher person of embodiment value, it is better to grab ground braking safe effect.The loss tangent of the sulfuration sheet plate film gained of each embodiment is as shown in table one and table two.
Table one
| Embodiment 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| First properties-correcting agent | M1 | M1 | TEOS | TMOS |
| First properties-correcting agent/conjugated diene rubber-lithium (mol ratio) | 2.0 | 0.5 | 1.0 | 1.0 |
| Second properties-correcting agent | M2 | - | - | - |
| Second properties-correcting agent/conjugated diene rubber-lithium (mol ratio) | 3.0 | - | - | - |
| Initial molecular weight (Mi, 10kg/mole) | 26.3 | 26.0 | 24.3 | 23.7 |
| Coupling rate (polymers soln) % | 19 | 58 | 19 | 41 |
| MV (after direct hot roller desolventizing) | 49 | 71 | 46 | 54 |
| Coupling rate (stripping is also dry rear) % | 55 | 61 | - | - |
| MV (stripping is also dry rear) | 75 | 61 | - | - |
| MV (after storage test) | 76 | 62 | 53 | 91 |
| Styrene content % | 20 | 21 | 21 | 21 |
| Contents of ethylene % | 63 | 63 | 64 | 63 |
| Tg°C | -23 | -24 | -23 | -24 |
| Akron abrasion rate (Idex) | 115 | 120 | 100 | 105 |
| tanδ(0°C) | 164 | 155 | 100 | 103 |
| tanδ(60°C) | 132 | 94 | 100 | 104 |
Table two
| Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| First properties-correcting agent | M1 | M1 | M1 |
| First properties-correcting agent/conjugated diene rubber-lithium (mol ratio) | 2.0 | 2.0 | 2.0 |
| Second properties-correcting agent | M2 | M3 | M3 |
| Second properties-correcting agent/conjugated diene rubber-lithium (mol ratio) | 2.0 | 3.0 | 2.0 |
| Initial molecular weight (Mi, 10kg/mole) | 26.0 | 26.0 | 26.1 |
| Coupling rate (polymers soln) % | 31 | 32 | 31 |
| MV (after direct hot roller desolventizing) | 58 | 56 | 58 |
| Coupling rate (stripping is also dry rear) % | 69 | 68 | 73 |
| MV (stripping is also dry rear) | 80 | 80 | 80 |
| MV (after storage test) | 82 | 81 | 82 |
| Styrene content % | 20 | 20 | 20 |
| Contents of ethylene % | 63 | 63 | 63 |
| Tg°C | -24 | -24 | -24 |
| Akron abrasion rate (Idex) | 172 | 133 | 175 |
| tanδ(0°C) | 110 | 111 | 119 |
| tanδ(60°C) | 106 | 106 | 105 |
Above Akron abrasion rate table wear resistant, tan δ (0 ° of C) shows wetland earth-grasping force, and tan δ (60 ° of C) shows rolling resistance, and three's numerical value out of the ordinary gets over Gao Yuejia.
In table one and table two, mooney viscosity (MV, Mooney Viscosity) is preheating 1 minute and measures under the condition continuing 4 minutes at 100 DEG C.Mooney viscosity measure time point have: modified-reaction complete and desolventizing after (after being labeled as direct desolventizing); Steam stripped also (is labeled as stripping also dry rear) after mechanical drying; And after 90 ° of C, relative humidity 80% and storage test in 40 hours (being labeled as after storage test).MV (stripping dry after) and MV (after storage test) numeric ratio more roughly equal, represent the improvement of the stability of mooney viscosity.Coupling rate (Coupling Ratio (C/R%)) measures with hydrogel permeation layer analyzer (GPC) and refractometer, refer to that molecular weight accounts for the ratio of whole polymkeric substance higher than the polymkeric substance of molecular weight before non-coupling, using tetrahydrofuran (THF) (tetrahydrofuran) as mobile phase (mobile phase) in time measuring.Coupling rate measures time point to be had: the polymers soln state (being labeled as polymers soln) after modified-reaction completes; Steam stripped also (is labeled as stripping also dry rear) after mechanical drying.Other characteristics are then tested with technology known in those skilled in the art, and such as styrene content, contents of ethylene measure with fourier transform infrared spectrometer (FTIR).Akron abrasion (Akron abrasion) measures wear resistant, uses Akron abrasion machine, measure in loading be 6 pounds, wear loss under 3300 rotation numbers.Index is higher, and to represent wear loss fewer.
Although the present invention with preferred embodiment openly as above; so it is not intended to limiting the invention, any those skilled in the art, without departing from the spirit and scope of the present invention; change and retouching when doing, therefore protection scope of the present invention is when being as the criterion with the appending claims person of defining.
Claims (25)
1. a manufacture method for modified conjugated diene rubber, comprises:
Step (a): the conjugated diene rubber of alkali metal containing ion and the first properties-correcting agent are reacted, this first properties-correcting agent has following structural formula (I)
Wherein R
1, R
2, R
3be selected from independently of one another containing C
1~ C
12alkyl and thiazolinyl and C
6~ C
12aromatic base, and R
4be selected from C
1~ C
12alkyl, thiazolinyl, alkoxyl group and C
6~ C
12aromatic base;
Step (b): add the second properties-correcting agent after this step (a), this second properties-correcting agent has following structural formula (II)
HO－R
5－Y (II)
Wherein R
5be selected from C
1~ C
12alkylidene group, alkenylene, alicyclic radical and C
6~ C
12aromatic base, Y is selected from C
1~ C
12oxy radical and C
1~ C
12nitrogen-containing group, Y is with its Sauerstoffatom or its nitrogen-atoms directly and R
5carbon atom combine; And
Step (c): while this step (b) is carried out or before or after add water molecules.
2. the manufacture method of modified conjugated diene rubber according to claim 1, wherein Y has alkyl, thiazolinyl or aromatic base and connects this Sauerstoffatom or this nitrogen-atoms.
3. the manufacture method of modified conjugated diene rubber according to claim 1, wherein this R
1, R
2, R
3be selected from methyl, ethyl and propyl group independently of one another.
4. the manufacture method of modified conjugated diene rubber according to claim 1, wherein this R
4be selected from methyl, ethyl and propyl group.
5. the manufacture method of modified conjugated diene rubber according to claim 1, wherein this second properties-correcting agent is 3-methoxyl group phenol or dimethylaminoethanol.
6. the manufacture method of modified conjugated diene rubber according to claim 1, wherein the molar ratio of the conjugated diene rubber of this first properties-correcting agent and alkali metal containing ion is >=0.5.
7. the manufacture method of modified conjugated diene rubber according to claim 1, wherein the molar ratio of the conjugated diene rubber of this second properties-correcting agent and alkali metal containing ion is >=0.5.
8. the manufacture method of modified conjugated diene rubber according to claim 1, the method wherein adding water molecules in this step (c) comprises steam stripped.
9. the manufacture method of modified conjugated diene rubber according to claim 1, wherein this modified conjugated diene rubber records the first mooney viscosity through this step (c) after drying, again through 90 DEG C, record the second mooney viscosity after relative humidity 80% and storage test in 40 hours, the difference between this first mooney viscosity and second mooney viscosity is 1 or 2.
10. the manufacture method of modified conjugated diene rubber according to claim 1, wherein before step (a) is carried out, the initial number average molecular weight of the conjugated diene rubber of this alkali metal containing ion is 80kg/mole ~ 2000kg/mole.
The manufacture method of 11. modified conjugated diene rubber according to claim 1, wherein this through the coupling rate of this modified conjugated diene rubber of step (c) between 10% ~ 95%.
12. 1 kinds of modified conjugated diene rubber, it is made with the manufacture method any one of claim 1 to 11.
13. 1 kinds of conjugated diene rubber compositions, comprise:
This modified conjugated diene rubber according to claim 12; And
Silicon-dioxide.
14. conjugated diene rubber compositions according to claim 13, wherein when the total amount of whole rubber constituents of this conjugated diene rubber composition is 100 weight part, the content of this modified conjugated diene rubber is more than 10 weight parts.
15. conjugated diene rubber compositions according to claim 13, wherein when the total amount of whole rubber constituents of this conjugated diene rubber composition is 100 weight part, the content of this silicon-dioxide is 10-200 weight part.
16. 1 kinds of modified conjugated diene rubber, this modified conjugated diene rubber is following structural formula (III) or structural formula (IV):
The polymeric chain that D is formed for conjugated diene unit or conjugated diene unit and vinyl aromatic unit,
Wherein R
4be selected from C
1~ C
12alkyl, thiazolinyl, alkoxyl group and C
6~ C
12aromatic base, R
5be selected from C
1~ C
12alkylidene group, alkenylene, alicyclic radical and C
6~ C
12aromatic base, Y is selected from C
1~ C
12oxy radical and C
1~ C
12nitrogen-containing group, Y is with its Sauerstoffatom or its nitrogen-atoms directly and R
5carbon atom combine.
17. modified conjugated diene rubber according to claim 16, wherein, Y has alkyl, thiazolinyl or aromatic base and connects this Sauerstoffatom or this nitrogen-atoms.
18. modified conjugated diene rubber according to claim 16, wherein these R
4be selected from methyl, ethyl and propyl group.
19. modified conjugated diene rubber according to claim 16 ,-the O-R wherein in this structural formula (III) and this structural formula (IV)
5-Y is-O-(C
6h
4)-OCH
3or-O-CH
2cH
2n (CH
3)
2.
20. modified conjugated diene rubber according to claim 16, wherein the coupling rate of this modified conjugated diene rubber is between 10% ~ 95%.
21. modified conjugated diene rubber according to claim 16, the wherein process that contacts through water of this modified conjugated diene rubber.
22. modified conjugated diene rubber according to claim 21, the wherein process that contacts through this water of this modified conjugated diene rubber record the first mooney viscosity after drying, again through 90 DEG C, record the second mooney viscosity after relative humidity 80% and storage test in 40 hours, the difference between this first mooney viscosity and second mooney viscosity is 1 or 2.
23. 1 kinds of conjugated diene rubber compositions, comprise:
This modified conjugated diene rubber any one of claim 16-22; And
Silicon-dioxide.
24. conjugated diene rubber compositions according to claim 23, wherein when the total amount of whole rubber constituents of this conjugated diene rubber composition is 100 weight part, the content of this modified conjugated diene rubber is more than 10 weight parts.
25. conjugated diene rubber compositions according to claim 23, wherein when the total amount of whole rubber constituents of this conjugated diene rubber composition is 100 weight part, the content of this silicon-dioxide is 10-200 weight part.
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| KR20130069368A (en) | 2013-06-26 |
| EP2604631A1 (en) | 2013-06-19 |
| US9260537B2 (en) | 2016-02-16 |
| JP5860797B2 (en) | 2016-02-16 |
| US20130158192A1 (en) | 2013-06-20 |
| KR101543738B1 (en) | 2015-08-11 |
| CN103159869A (en) | 2013-06-19 |
| EP2604631B1 (en) | 2015-04-08 |
| JP2013124370A (en) | 2013-06-24 |
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